JPH06313170A - Phenylbicyclohexane derivative - Google Patents

Abstract

PURPOSE:To obtain the subject deriv. which has a cyclohexylcyclohexylbenzene backbone, a lowered m.p., and an improved compatibility with other liq. crystal compds. and hardly crystallizes even at a low temp. by mixing at least two specific compds. CONSTITUTION:At least two compds. selected from those represented by the formula [wherein R<1> is 1-12C alkyl; Y<1> and Y<2> are each H or F; Z is F, Cl, cyano, R<2>, OR<2>, CF3, OCF3, OCF2H, or OCH2CF3; R<2> is 1-12C alkyl or 2-12C alkenyl; X<1> to X<3> are each H or D (deuterium) provided at least one of X<1> to X<3> is D; and the cyclohexane rings are in trans-configuration] are mixed in such a manner that each of the compds. mixed has the number of D's and/or the positions of D's different from those of other compds. mixed and that each has the same R<1>, Y<1>, Y<2>, and Z as those of other compds.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel liquid crystalline compound useful as an electro-optical liquid crystal display material, which is a mixture of phenylbicyclohexane derivatives having a deuterium-substituted cyclohexane ring, and a liquid crystal composition containing the same. And a mixture of deuterium-substituted cyclohexanone derivatives useful as an intermediate for the production of phenylbicyclohexane derivatives substituted by the deuterium atom.

[0002]

2. Description of the Related Art Liquid crystal display devices have come to be used in watches, calculators, various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions and the like. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, and FLC (ferroelectric liquid crystal). ), Etc., and as the drive system, the conventional static drive has become more common and multiplex drive has become more common, and the simple matrix system and recently the active matrix system have been put into practical use.

Various characteristics are required as a liquid crystal material according to these display system and drive system. (1)
The wide temperature range of the liquid crystal phase and (2) the small viscosity are important required characteristics common to all the methods. More specifically, as the characteristics of (1), it is important that (1a) the nematic phase maximum temperature (T _NI ) is high, and (1b) that the melting point is low so that phase separation such as crystallization or precipitation does not easily occur. .

Up to the present, no liquid crystal compound which alone satisfies such required properties has been known, and it is actually used as a mixture of various liquid crystal compounds. Although a wide variety of liquid crystal compounds have been developed so far, cyclohexylcyclohexylbenzene (CCP) is a compound that can relatively satisfy the above conditions (1) and (2).
Compounds having a skeleton are relatively often used.

The compound having this CCP skeleton is T _NI
Is relatively high and the viscosity is relatively low as a tricyclic compound. However, when this compound was added to the composition, the effect of lowering the melting point of the composition was not particularly excellent as compared with other liquid crystal compounds.

In order to lower the melting point of the liquid crystal material, it is effective to mix a large number of liquid crystal compounds and increase the number of components in the composition. For example, in order to maintain the characteristics of the compound having a CCP skeleton and increase the number of components to lower the melting point, the number of homologues having a CCP skeleton and different in the number of carbon atoms of the terminal alkyl group is used. A method of adding seeds is used. However, even with this method, there is a limit in suppressing the precipitation of crystals in the low temperature region.

[0007]

The problem to be solved by the present invention is to have a CCP skeleton, and when added to the composition, lower the melting point without adversely affecting other properties, or lower the temperature. However, it is an object of the present invention to provide a liquid crystal compound in which crystals are less likely to precipitate and which is excellent in compatibility with other liquid crystal compounds, a production intermediate thereof, and a liquid crystal composition containing the liquid crystal compound.

[0008]

In order to solve the above-mentioned problems, the present invention has the general formula (I)

[0009]

[Chemical 3]

(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, preferably a linear alkyl group having 1 to 7 carbon atoms. X ¹ , X ² and X ³ are each independently. To
Represents a hydrogen atom (H) or a deuterium atom (D),
At least one of X ¹ , X ² and X ³ represents a deuterium atom (D). Y ¹ and Y ² each independently represent a hydrogen atom or a fluorine atom. Z represents a fluorine atom, a chlorine atom, a cyano ^{group, -R 2, -OR 2, -CF} 3, -OCF 3,
-OCF represents ₂ H or -OCH ^₂ CF _3, R ₂ represents an alkyl group having 1 to 12 carbon atoms, of which fluorine atom, a chlorine atom, a cyano group, a linear 1 to 7 carbon atoms alkoxyl group, -OCF ₃ or -OCH ₂ CF ₃ preferred. The cyclohexane ring has a trans configuration. ), Two or more compounds selected from the group consisting of deuterium-substituted phenylcyclohexane derivatives are (1) different in deuterium atom (D) number and / or substitution position, and (2) mutually R ¹ , Y ¹ , Y ² and Z
A mixture of two or more compounds selected from the group consisting of the compounds represented by the above general formula (I).

As mentioned above, the compound of the general formula (I) of the present invention is
The characteristics of the compound are X in each compound ¹, X²And X³Haso
Each independently, a hydrogen atom (H) or a deuterium atom (D)
And at least one of them is a deuterium atom.
(D). Therefore, R¹, Y¹, Y²And Z
Are the same, and X¹, X²And X³Only for different compounds
In this case, the compound of the general formula (I) includes stereoisomers such as X
¹, X²And X³There are 10 compounds depending on
You will get it.

However, as will be described later, in the production process of the compound of the general formula (I), it is safe to use some of these compounds in a mixture. On the contrary, when used as a mixture, it has features that excellent precipitation characteristics such as precipitation of crystals in a low temperature region and improvement of compatibility with other liquid crystal compounds can be obtained.

In the mixture of general formula (I) according to the invention:
In order to obtain the excellent effects as described above, the general formula (I)
The total number of deuterium atoms (D) in the two or more compounds represented by is 5 with respect to the total number of X ¹ , X ² and X ^3.
It is preferably 0% or more.

It is already known that a hydrogen atom (H) is replaced with a deuterium atom (D) in a liquid crystal compound, and there are several reports as shown below. 1) H. Gasparoux et al., Ann.ReV.Phys.Chem., 27, 175 (1976) 2) GWGray et al., Mol.Cryst.Liq.Cryst., 41, 75 (1977) 3) AJ Leadbetter et al., J. Phys . [Paris] coll C3, 40,
125 (1979) 4) A. Kolbe et al., Z. Naturforsch., 23a, 1237 (1968) 5) JD Rowell et al., J. Chem. Phys., 43, 3442 (1965) 6) WD Philips et al., J. Chem. Phys ., 41, 2551 (1964) 7) AF Martins et al., Mol.Cryst.Liq.Cryst., 14, 85 (197
1) 8) ET Samulski et al., Phys. Rev. Lett., 29, 340 (1972).

In these reports, except for the case where the hydrogen atom (H) in the carboxyl group of 4-alkoxybenzoic acid was replaced with a deuterium atom (D) (reference (1)), the hydrogen atom in the side chain ( H) is replaced by a deuterium atom (D), or a hydrogen atom (H) of the benzene ring is replaced by a deuterium atom (D), and the compounds of the general formula (I) of the present invention are the same. No example of a compound in which the hydrogen atom (H) of the cyclohexane ring was replaced with a deuterium atom (D) was known.

The mixture of the general formula (I) of the present invention can be produced, for example, as follows. General formula (I
I)

[0017]

[Chemical 4]

(Where R is¹Is the same as in general formula (I)
The same meaning, X¹, X², X³And X ^FourAre independent
Represents a hydrogen atom (H) or a deuterium atom (D)
However, at least one of them represents a deuterium atom (D).
The cyclohexane ring is in the trans configuration. )
Deuterium-substituted 4- (4-alkylcyclohexyl)
Xyl) cyclohexanone derivative
Two or more compounds that are (1) mutually deuterium atoms (D)
Different in the number and / or substitution position, and (2) are mutually R
¹Are the same, said general formula (II)
Two or more kinds selected from the group consisting of compounds represented by
By using a mixture of compounds as an intermediate
Of an unsubstituted CCP derivative that is not deuterium substituted
It can be manufactured in the same manner as the manufacturing method.

More specifically, it can be obtained according to the following example. In b) the general formula (I), Z = F, R 2, -OR 2,
For compounds which are -CF ₃ or -OCF ₃

[0020]

[Chemical 5]

The 4-bromo compound of the general formula (IV) is directly added with magnesium as a Grignard reaction agent to obtain the general formula (II).
The resulting cyclohexanol derivative is dehydrated into a cyclohexene derivative, then hydrogenated, and isomerized to a trans isomer, if necessary,
It can be obtained by separating and removing the cis form. B) In the general formula (I), Z = -OR ² or -OC
In the case of a compound that is H ₂ CF ₃

[0022]

[Chemical 6]

In the above item a), 4-of the general formula (IV)
In the bromo compound, a compound in which Z = -OCH ₃ is used, and in the general formula (I), Z =
To give compound is -OCH _3. Demethylate this by using trimethylsilyl iodide, boron tribromide, aluminum chloride, hydrobromic acid, etc.,
A phenol derivative of the general formula (V) is obtained. In the presence of a base, the compound of the general formula (V) is treated with R ² W or WCH ₂ C.
By reacting with F ₃ (wherein W represents a bromine atom, an iodine atom or a leaving group such as a p-toluenesulfonyl group), Z is —OR ² or —OCH ₂ CF _3; The compounds of I) can be obtained.

Alternatively, the phenol derivative of the general formula (V) can also be obtained by reacting the aniline derivative of the general formula (X) described below with sodium nitrite in an aqueous sulfuric acid solution to form a diazonium salt, and decomposing the salt. be able to. C) formula (I), when the compound is Z = -OCF ₂ H

[0025]

[Chemical 7]

It can be obtained by converting the compound of the general formula (V) obtained in the above (b) into a formate ester and fluorinating it with dimethylaminosulfur trifluoride (DAST) or the like. D) In the case of the compound in which Z = -CN in the general formula (I)

[0027]

[Chemical 8]

In the above-mentioned a), by using the compound of the general formula (VI) in which Z = H in the compound of the general formula (IV) in place of the compound of the general formula (IV), the compound of the general formula (I) is obtained. A compound of general formula (VII) is obtained in which Z = H.

[0029]

[Chemical 9]

The compound of the general formula (VII) is reacted with oxalic acid chloride in the presence of a Lewis acid to give an acid chloride, and then reacted with ammonia to give the compound of the general formula (VIII).
Amide is obtained. By dehydrating this with thionyl chloride or the like, a compound having Z = -CN in the general formula (I) can be obtained.

[0031]

[Chemical 10]

Alternatively, the acid chloride which is an intermediate thereof is obtained by acetylating a compound of the general formula (VII) and then oxidizing it with bromine in an aqueous alkaline solution to give a carboxylic acid of the general formula (IX), followed by thionyl chloride and the like. It can also be obtained by reacting with the chlorinating agent.

[0033]

[Chemical 11]

Alternatively, by directly iodizing the compound of the general formula (VII) with iodine / periodic acid and then reacting it with copper (I) cyanide, the compound of the general formula (I) in which Z = -CN is obtained. Can be obtained. E) In the case of a compound of the general formula (I) where Z = Cl

[0035]

[Chemical 12]

An amide of the general formula (VIII) can be reacted with bromine in an alkaline aqueous solution to obtain an aniline derivative of the general formula (X), which can be reacted with sodium nitrite in the presence of hydrochloric acid to form a diazonium salt. By decomposing this with copper (I) chloride, a compound in which Z = Cl in the general formula (I) can be obtained.

In the above production process, when at least one of Y ¹ and Y ² in the general formula (I) is F, it is difficult to obtain the corresponding compound of the general formula (IV) in the above process a). In some cases. Alternatively, in the step (d), it may be difficult to selectively introduce the substituent Z at a desired position.

Therefore, in such a case, as shown below, the intermediate compound of the general formula (VII) is lithiated with butyllithium or the like to give a phenyllithium derivative of the general formula (XI), which is The compound of the general formula (IX) can be obtained by direct alkylation (a compound in which Z = R ² in the general formula (I)) or reaction with carbon dioxide.
Can be obtained by the method described above.

[0039]

[Chemical 13]

The general formula (II) used as an intermediate here
Deuterium-substituted 4- (trans-4-alkylcyclohexyl) cyclohexanone of is also a novel compound,
The present invention also provides mixtures of this compound.

The characteristic of the mixture of the general formula (II) is that X ¹ , X ² , X ³ and X ⁴ in each compound independently represent a hydrogen atom (H) or a deuterium atom (D) as described above. As shown, at least one of X ^{1 to} X ⁴ is a deuterium atom (D).

By the way, in the above-mentioned method for producing a mixture of the general formula (I), one deuterium atom (D) in X ^{1 to} X ⁴ in the general formula (II) is the same as in the general formula (I). It is clear that it is lost by dehydration during the production of the mixture, and is subsequently replaced by a hydrogen atom (H) by the subsequent hydrogenation. At this time, since there is no distinction between X ^{1 to} X ⁴ , it may be considered that X ⁴ is eliminated and replaced with a hydrogen atom (H) for the sake of convenience. Therefore, the compound of the general formula (I) of the present invention also has this. Correspondingly, only X ^{1 to} X ³ are shown, and the position corresponding to X ⁴ has a structure in which a hydrogen atom is replaced.

In order to obtain excellent properties of a mixture of two or more compounds selected from the group consisting of the compounds represented by formula (I) of the present invention, the total number of deuterium atoms (D) in this mixture is required. Is 50 for the total number of X ^{1 to} X ^3.
% Or more is preferable.

Therefore, even in a mixture of two or more compounds selected from the group consisting of the corresponding compounds of the general formula (II), the total number of deuterium atoms is 70% with respect to the total number of X ^{1 to} X ^4. The above is preferable.

The compound of the general formula (II) is a compound of the general formula (III) which is not substituted with the corresponding deuterium.

[0046]

[Chemical 14]

It can be obtained by dissolving 4- (trans-4-alkylcyclohexyl) cyclohexanone in aprotic solvent such as dichloromethane and reacting it with heavy water in the presence of a base such as alcoholate. The reaction is preferably carried out at room temperature to a temperature at which the solvent is refluxed, and in order to promote the reaction, it is also preferable to coexist with a quaternary ammonium salt such as tetrabutylammonium bromide.

Of the compounds of general formula (I) thus obtained
Examples and their phase transition temperatures are given in Tables 1 and 2. still,
For reference, the compounds of general formula (I)
X ¹~ X³A phase of a compound in which no deuterium is substituted
The literature value of the transition temperature is also shown.

[0049]

[Table 1]

[0050]

[Table 2]

(In the table, C represents a crystalline phase, Sm represents a smectic phase, N represents a nematic phase, and I represents an isotropic liquid phase.) The mixture of the general formula (I) of the present invention corresponds to In comparison with the compound not substituted with deuterium, the temperature range of the nematic phase is almost not narrowed, and the smectic phase is disappeared or very narrowed.

Further, the liquid crystal composition containing two or more compounds selected from the group consisting of the compounds of the general formula (I) is characterized in that crystals are hard to precipitate even at low temperatures.
For example, the matrix liquid crystal (A) that is currently widely used

[0053]

[Chemical 15]

(In the formula, the cyclohexane ring represents a trans configuration and "%" represents "% by weight") 85% by weight
And (No. 1) in Table 1

[0055]

[Chemical 16]

A liquid crystal composition (B) consisting of 15% by weight of the mixture of was prepared and stored at -20 ° C.
No precipitation of crystals was observed even after a lapse of months. The mixture of (No. 1) is represented by X ¹ in the general formula (I),
The total number of deuterium atoms (D) with respect to the total number of X ² and X ³ (hereinafter referred to as D conversion rate) was about 84%.

On the other hand, the base liquid crystal (A) was 85% by weight.
And the compound of formula (R-1) not substituted by deuterium in the compound of (No. 1) above.

[0058]

[Chemical 17]

When a mixed liquid crystal (C) containing 15% by weight of the compound of (1) was prepared and stored at -20 ° C in the same manner, precipitation of crystals was observed after 5 days. From this, a mixture of compounds of general formula (I) according to the invention is
It can be understood that it has excellent compatibility with other liquid crystal compounds, and particularly excellent compatibility at low temperatures, so that crystals are less likely to precipitate as compared with conventional liquid crystal compounds and it is extremely useful as a practical liquid crystal. .

[0060]

EXAMPLES The present invention will be further described below by showing Examples of the present invention. However, the invention is not limited to these examples.

Regarding the structure of the compound, a known compound not deuterated was compared with a capillary gas chromatograph and a thin layer chromatograph to show the same retention time (or Rf value), and a nuclear magnetic resonance spectrum ( NM
R), mass spectrum (MS), infrared absorption spectrum (IR). The D conversion rate was measured by NMR. The NMR used for the measurement was JEOL Ltd.
It is made by JNM-GSX400 (400 MHz ¹ H).

D before the compound name and structural formula
₄ - is a mixture of compounds at least one of the four hydrogen atoms of the 2-position and 6-position of the cyclohexane ring directly linked with the benzene ring is deuterated, d ₃ - is the three hydrogen atoms It represents a mixture of compounds in which at least one is deuterium substituted.

Example 1 Deuteration of 4- (trans-4-propylcyclohexyl) cyclohexanone

[0064]

[Chemical 18]

6.1 g of sodium methoxide was added to heavy water (D
The conversion rate: 99.8%) was dissolved in 50 ml. To this was added 50 g of 4- (trans-4-propylcyclohexyl) cyclohexanone dissolved in 50 ml of dichloromethane,
Further, 0.25 g of tetrabutylammonium bromide was added, and the mixture was heated and stirred at the reflux temperature of the solvent for 13 hours. After cooling, the organic layer was separated, and the aqueous layer was extracted with dichloromethane and then collected. The organic layers were combined, washed with water, and dehydrated and dried over anhydrous sodium sulfate.

[0066] The solvent d _4-4-2 and 6 positions of distilled off to cyclohexanone ring is deuterated the (trans-4
-Propylcyclohexyl) cyclohexanone 50.7
g was obtained. The deuteration ratio (D conversion ratio) measured by NMR was about 82%.

[0067] (Example 2) 4 in the same manner as deuterated Example 1 (trans-4-butylcyclohexyl) cyclohexanone, d ₄ to the 2-position and 6-position of cyclohexanone ring is deuterated 4- (Trans-4-butylcyclohexyl) cyclohexanone was obtained. NMR
According to the measurement of the D conversion rate, it was about 85%.

[0068] (Example 3) d _{3-3,4-difluoro-1-} [trans-4- (trans-4-propyl) cyclohexyl] Synthesis of benzene

[0069]

[Chemical 19]

[0070] _{(3-a) d 4 -1-} (3,4- difluorophenyl) -4- (trans-4-propyl) cyclohexyl-1-cyclohexanol synthesized dry tetrahydrofuran (THF) form scraped into 5ml 2.8 g of magnesium was added. 21 g of 1-bromo-3,4, -difluorobenzene in THF7 was added to this mixed solution.
The 0 ml solution was added dropwise at a rate that maintained a gentle reflux. After the dropwise addition was completed, the mixture was stirred for 2 hours and then left to cool. Under ice-cooling, d ₄ 4 obtained in Example 1 (trans-4-
Propylcyclohexyl) cyclohexanone 20 g T
The HF 50 ml solution was added dropwise over 40 minutes, taking care not to let the internal temperature exceed 40 ° C. After stirring at room temperature for another hour,
With stirring, dilute hydrochloric acid was added until the aqueous layer became slightly acidic.
The mixture was extracted with 100 ml of ethyl acetate, the organic layer was washed with water and then with saturated saline, and dehydrated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure d _4-1- (3,4-difluorophenyl) -4- (trans-4-propyl) crude crystals of cyclohexyl-1-cyclohexanol 31.
6 g was obtained.

(3-b) d ₃ -3,4-difluoro-
1- [4- (trans-4-propylcyclohexyl)
Cyclohexen-1-yl] d _4-1- (3,4-difluorophenyl) obtained in the above (3-a) benzene-4 the total amount of (trans-4-propyl) cyclohexyl-1-cyclohexanol Was dissolved in 80 ml of toluene, and 0.8 g of potassium hydrogen sulfate was added. The mixture was heated under reflux for 3 hours with stirring while removing distilled water. After allowing to cool to room temperature, it was washed with water, saturated aqueous sodium hydrogen carbonate solution, water and then saturated saline, and dehydrated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and d
₃ -3,4-difluoro-1- [4- (trans-4-
Propylcyclohexyl) cyclohexen-1-yl]
29.0 g of crude benzene crystals were obtained.

(3-c) d ₃ -3,4-difluoro-
Synthesis of 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene d ₃ − obtained in (3-b) above in an autoclave
29.0 g of 3,4-difluoro-1- [4- (trans-4-propylcyclohexyl) cyclohexen-1-yl] benzene was dissolved in 140 ml of ethyl acetate. 2.6 g of palladium carbon was added to this solution, and the hydrogen pressure was 4K.
The mixture was stirred at g / cm ² for 3 hours at room temperature. The catalyst was removed by celite filtration, and the solvent was distilled off under reduced pressure, d ₃ -3,
4-difluoro-1- [trans-4- (trans-4
- to obtain a 36/56 mixture 27.8g of propyl) cyclohexyl] benzene and d _{3-3,4-difluoro-1-} [cis-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene. Recrystallization from ethanol, d _{3-3,4-difluoro-1-} [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene 5.8g
Got Next, the mother liquor was concentrated to obtain d ₃ -3,4-
Difluoro-1- [trans-4- (cis-4-propylcyclohexyl) cyclohexyl] benzene 22.0
g was dissolved in 90 ml of dimethyl sulfoxide (DMSO), 3.1 g of potassium t-butoxide was added, and the mixture was stirred at 80 ° C. for 3 times.
Reacted for hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was neutralized with diluted hydrochloric acid, and the reaction product was extracted twice with toluene. The toluene layer was washed with water, then brine, was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure, d _{3-3,4-difluoro-1-} [trans-4
- (trans-4-propylcyclohexyl) cyclohexyl] benzene and d _{3-3,4-difluoro-1-}
[Cis-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene 70/5 mixture 20.
9 g was obtained. This was recrystallized from ethanol and d ₃ −
11.7 g of 3,4-difluoro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained. (Total yield: 17.5 g) Phase transition temperature: 42.8 ° C. (Cr → N), 118.7 ° C.
(N → I)

(Comparative Example 1) 3,4-difluoro-1-
Synthesis of [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene In Example 3, instead of d ₄ -4- (trans-4-propylcyclohexyl) cyclohexanone, non-deuterated 4- ( Undeuterated 3,4-difluoro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl was prepared in exactly the same manner as in Example 3 except that trans-4-propylcyclohexyl) cyclohexanone was used. ] I got benzene. The phase transition temperature of this compound was as follows. Phase transition temperature: 43.9 ° C (Cr → N), 124.3 ° C
(N → I) The values described in the literature for the phase transition temperature of this compound were as follows. Phase transition temperature (reference value): 45 ° C (Cr → N), 124 ° C
(N → I)

[0074] (Example 4) in d _{3-3,4-difluoro-1-} [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] Synthesis Example 3 of benzene, d ₄ 4- (trans - 4-propylcyclohexyl) cyclohexanone instead of d ₄ −
D ₃ − was obtained in the same manner as in Example 3 except that 4- (trans-4-butylcyclohexyl) cyclohexanone was used.
3,4-Difluoro-1- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] benzene was obtained. The phase transition temperature of this compound is shown in Table 1.

[0075] (Example 5) Synthesis of d ₃ -3,4,5-trifluoro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene (5-a) d ₄ -1- (3,4,5-trifluorophenyl) -4- (trans-4-propyl) cyclohexyl-1-d ₄ 4 obtained in synthesis example 1 of cyclohexanol (trans-4-propyl-cyclohexyl) cyclohexanone 20.0 g and 3,4,5-trifluoro-1-bromobenzene 22.
From 0 g, in the same manner as in (3-a) above, d ₄ -1-
35.2 g of (3,4,5-trifluorophenyl) -4- (trans-4-propyl) cyclohexyl-1-cyclohexanol was obtained.

(5-b) Synthesis of d ₃ -3,4,5-trifluoro-1- [4- (trans-4-propylcyclohexyl) cyclohexen-1-yl] benzene Obtained in (5-a) above. is d _4-1- (3,4,5-trifluorophenyl) -4- (trans-4-propyl) using the total amount of cyclohexyl-1-cyclohexanol, in the same manner as in (3-b), d ₃ -3,4,5
28.6 g of -trifluoro-1- [4- (trans-4-propylcyclohexyl) cyclohexen-1-yl] benzene were obtained. Further, the product was recrystallized from ethanol to obtain 22.6 g of a purified product.

[0077] (5-c) obtained in d ₃ -3,4,5-trifluoro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene Synthesis of (5-b) with the total amount of d ₃ -3,4,5-trifluoro-1- [4- (trans-4-propyl-cyclohexyl) cyclohexen-1-yl] benzene, the hydrogenation in the same manner as in the above (3-c) Done, d ₃
-3,4,5-Trifluoro-1- [trans-4-
(Trans-4-propylcyclohexyl) cyclohexyl] benzene and d ₃ -3,4,5-trifluoro -
60/40 mixture of 1- [cis-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene 2
2.5 g was obtained. This was recrystallized from ethanol and d ₃
-3,4,5-Trifluoro-1- [trans-4-
11.5 g of (trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained. The phase transition temperature of this compound is shown in Table 1.

[0078] (Example 6) Synthesis of d ₃ -3,4,5-trifluoro-1- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] benzene (6-a) d ₄ -1- (3,4,5-trifluorophenyl) -4- (trans-4-butyl) cyclohexyl-1-d ₄ 4 obtained in example 2 of cyclohexanol (trans-4-butylcyclohexyl) cyclohexanone 20.0g and 3,
2,5-trifluoro-1-bromobenzene 21.5 g
From (3-a) to d ₄ -1- (3,4,5
-Trifluorophenyl) -4- (trans-4-butylcyclohexyl) -1-cyclohexanol 34.2
g was obtained.

(6-b) Synthesis of d ₃ -3,4,5-trifluoro-1- [4- (trans-4-butylcyclohexyl) cyclohexen-1-yl] benzene Obtained in the above (6-a). was d _4-1- (3,4,5-trifluorophenyl) -4- (trans-4-butylcyclohexyl) -1-using the total amount of cyclohexanol, in the same manner as in (3-b), d ₃ -3,4,5-
Trifluoro-1- [4- (trans-4-butylcyclohexyl) cyclohexen-1-yl] benzene 2
8.1 g was obtained.

(6-c) Synthesis of d ₃ -3,4,5-trifluoro-1- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] benzene Obtained in (6-b) above. d ₃ -3,4,5-trifluoro-1 using [4- (trans-4-butylcyclohexyl) cyclohexen-1-yl] benzene 27.9 g, except for using Raney nickel as the catalyst described above (3- Hydrogenation is carried out in the same manner as in c), and d ₃ -3,
4,5-trifluoro-1- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] benzene and d ₃ -3,4,5-trifluoro-1- [cis -
24.4 g of a 58/42 mixture of 4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained. Recrystallization from ethanol, d ₃ -3,
7.3 g of 4,5-trifluoro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained. Mixture recovered from mother liquor (48
/ 52) (16.6 g) was dissolved in N, N-dimethylformamide (DMF) (160 ml), potassium t-butoxide (1.0 g) was added, and the mixture was reacted at room temperature for 3 hours. Post-treatment is carried out in the same manner to give d ₃ -3,4,5-trifluoro-1-
[Trans-4- (trans-4-butylcyclohexyl) cyclohexyl] benzene and d ₃ -3,4,5-trifluoro-1- [cis-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene 97 /
13.9 g of 3 mixture was obtained. Which was recrystallized from ethanol to give the d ₃ -3,4,5-trifluoro-1- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] benzene 11.5 g. (Total yield: 18.8 g) The phase transition temperature of this compound was as follows. Phase transition temperature: 64 ° C. (Cr → N), 91 ° C. (N → I) 3,4,5-trifluoro-1 without deuterium substitution
The phase transition temperatures of-[trans-4- (trans-4-butylcyclohexyl) cyclohexyl] benzene reported in the literature (Proceedings of the 18th Liquid Crystal Symposium 1B504) were as follows. Phase transition temperature: melting point 58.6 ° C. (Cr → Sm), 64.1
C (Sm-N) C, 87.9 C (N-I)

Example 7 d ₃ -3-fluoro-4-
Synthesis of cyano-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene

[0082]

[Chemical 20]

(7-a) d ₃ -3-fluoro-1-
[Trans-4- (trans-4-propylcyclohexyl) cyclohexyl] d ₄ 4 obtained in Example 1 benzene (trans-4-propyl) cyclohexanone 5.0g and 3-
From 4.8 g of fluoro-1-bromobenzene, the above (3
-A) and were obtained in the same manner d _4-1- (3- fluorophenyl) -4- (trans-4-propyl) cyclohexyl-1-cyclohexanol 7.0 g. This was dehydrated in the same manner as in the above _{(3-b), d 3} -3- fluoro -
1- [4- (trans-4-propylcyclohexyl)
6.7 g of cyclohexen-1-yl] benzene were obtained.
Then, hydrogenation is carried out in the same manner as in the above (3-c), the isomers are separated by recrystallization, and d ₃ -3-fluoro-1
3.0 g of-[trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained.

[0084] (7-b) d ₃ -3- fluoro-4-cyano-1 Synthesis of trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene d _{3-3-fluoro-1-} [trans 3.0 g of -4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was dissolved in 30 ml of dichloromethane, and 2.6 g of anhydrous aluminum chloride was added and stirred. 1.3 g of oxalic acid dichloride was added dropwise over 30 minutes under ice cooling. After stirring at the same temperature for 1 hour, the temperature was returned to room temperature, the reaction solution was poured into ice water, the reaction product was extracted with hexane, and d ₃ −
2-fluoro-4- [trans-4- (trans-4-
Propylcyclohexyl) cyclohexyl] benzoic acid chloride was obtained. This was dissolved in 30 ml of dichloromethane, 10 ml of 30% aqueous ammonia was added, and the mixture was stirred for 1 hour. Hexane was added, the precipitated crystals were collected by filtration, diluted hydrochloric acid,
Saturated aqueous sodium hydrogen carbonate solution, water, and washed with cold methanol, and dried under reduced pressure, d _{3-2-fluoro-4-}
2.4 g of crystals of [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzamide were obtained. This was heated to reflux in 30 ml of thionyl chloride for 3 hours. After distilling off excess thionyl chloride under reduced pressure,
Toluene was added, saturated aqueous sodium hydrogen carbonate solution, water,
Then, it was washed with saturated saline and dehydrated and dried with anhydrous sodium sulfate. The solvent was distilled off, and recrystallized obtained crude product from ethanol, d _{3-3-fluoro-4-cyano} -1
1.8 g of-[trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained. The phase transition temperature and D conversion rate of this compound are shown in Table 1.

Example 8 d ₃ -4-cyano-1-
[Trans-4- (trans-4-propyl) cyclohexyl] Synthesis d ₄ 4- (trans-4-propyl-cyclohexyl) benzene
Cyclohexanone 5.0g and Bromobenzene 3.6g
In the same manner as in Example 7, d _3-4-cyano-1-
2.6 g of [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained. The phase transition temperature and D conversion rate of this compound are shown in Table 1.

Example 9 d ₃ -4-methoxy-1-
[Trans-4- (trans-4-propyl) cyclohexyl] Synthesis d ₄ 4- (trans-4-propyl-cyclohexyl) benzene
And cyclohexanone 5.0g and 4-bromoanisole 4.4g in the same manner as in Example 5, a d ₃ -4- methoxy-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene 3.0g Obtained. The phase transition temperature and D conversion rate of this compound are shown in Table 1.

Example 10 d ₃ -4-propyl-1
- [trans-4- (trans-4-propyl) cyclohexyl] Synthesis d ₄ 4- (trans-4-propyl-cyclohexyl) benzene
From 5.0 g of cyclohexanone and 4.7 g of 1-bromo-4-propylbenzene, d ₃ − was obtained in the same manner as in Example 5.
4-propyl-1- [trans-4- (trans-4-
2.8 g of propylcyclohexyl) cyclohexyl] benzene were obtained. The phase transition temperature and D conversion rate of this compound are shown in Table 1.

[0088] (Example 11) d ₃ -4- trifluoromethoxy -1-d ₄ 4 of [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene (trans-4-propyl-cyclohexyl)
And cyclohexanone 10.0g and 1-bromo-4-trifluoromethoxy benzene 11.9g in the same manner as in Example 6, d ₃ -4- trifluoromethoxy-1- [4
14.9 g of-(trans-4-propylcyclohexyl) cyclohexen-1-yl] benzene was obtained. This was hydrogenated with palladium carbon as a catalyst, d ₃ -4- trifluoromethoxy-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene and d ₃ -4- trifluoromethoxy-1 13.8 g of a 60/35 mixture of [trans-4- (cis-4-propylcyclohexyl) cyclohexyl] benzene was obtained. Which was recrystallized from ethanol to give white crystals 4.2g of d _{3-4-trifluoromethoxy-1-} [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene. The melting point of this compound is 6
The temperature was 3 ° C., a nematic phase was exhibited up to 147 ° C., and a smectic phase could not be confirmed. The D conversion rate of this compound is summarized in Table 1.

On the other hand, the non-deuterated 4-
Non-deuterated 4-trifluoromethoxy-1- [trans-4- (trans-4) synthesized from (trans-4-propylcyclohexyl) cyclohexanone
-Propylcyclohexyl) cyclohexyl] benzene had a melting point of 35 ° C, exhibited a smectic phase at 64.3 ° C or lower, and exhibited a nematic phase up to 151 ° C. Also,
According to the literature (Japanese Patent Publication No. 2-501311), the melting point is 39 ° C., and a smectic phase is shown at 68 ° C. or lower and a nematic phase is shown up to 148.6 ° C.

Example 12 d ₃ -4-fluoro-1
- [trans-4- (trans-4-propyl) cyclohexyl] Synthesis d ₄ 4- (trans-4-propyl-cyclohexyl) benzene
2.2 g of cyclohexanone and 1.9 g of 1-bromo-4-fluorobenzene were used to give d ₃ -4 in the same manner as in Example 5.
-Fluoro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene 1.
4 g was obtained. The phase transition temperature and the D conversion rate are summarized in Table 1.

Example 13 d ₃ -3-fluoro-4
-Chloro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene synthesis

[0092]

[Chemical 21]

(13-a) d ₃ -3-fluoro-4-
[Trans-4- (trans-4-propyl) cyclohexyl] d _3-2-fluoro-4 obtained in Example 7 aniline [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzamide 3.5 g of dioxane 50
Dissolve in 10 ml of 10% sodium hydroxide solution 300m
1 was added and the mixture was cooled to 0 ° C. Bromine (4.8 g) was added dropwise thereto over 1 hour, and the mixture was further stirred at 0 ° C. for 4 hours. An aqueous sodium hydrogen sulfite solution was added until the potassium iodide starch test paper did not turn blue, and the reaction product was extracted with toluene. After washing with dilute hydrochloric acid, water and saturated saline solution, the solvent is distilled off,
to obtain a d _{3-3-fluoro-4-} [trans-4- (trans-4-propyl) cyclohexyl] aniline 2.7 g.

[0094] (13-b) d ₃ -3- fluoro-4-
Chloro-1 the total amount of [trans-4- (trans-4-propyl) cyclohexyl] Synthesis d _{3-3-fluoro-4-benzene} [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] aniline It was dissolved in a small amount of acetonitrile, added to 50 ml of 35% hydrochloric acid, and cooled to 0 ° C. To this, 1.0 g of sodium nitrite was added little by little, and the mixture was further stirred for 2 hours.
This was slowly added dropwise to a saturated aqueous solution of 1.3 g of copper (I) chloride, and after completion of the addition, the mixture was stirred at 40 ° C. for 4 hours. After cooling down,
The mixture was extracted twice with toluene, and the organic layers were combined and washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine. The solvent was dehydrated and dried, and the crude product obtained by evaporation under reduced pressure was subjected to silica gel column chromatography (hexane / ethyl acetate =
20/1) as eluents, d _3-3-fluoro-4
-Chloro-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene 2.0
g was obtained. The phase transition temperature and the D conversion rate are summarized in Table 1.

(Example 14) d₃-3,5-difluo
Ro-4-chloro-1- [trans-4- (trans-4
-Propylcyclohexyl) cyclohexyl] benzene
Synthesis of d_Four-4- (trans-4-propylcyclohexyl)
Cyclohexanone 4.4 g and 3,5-difluoro-1
From 4.2 g of bromobenzene in the same manner as in Example 7,
d₃-3,5-difluoro-1- [trans-4- (to
Lance-4-propylcyclohexyl) cyclohexyl
Lu] benzene 4.5g is obtained, and d ₃-2,6-
Difluoro-4- [trans-4- (trans-4-p
Ropylcyclohexyl) cyclohexyl] benzamide
2.8 g was obtained. From now on, in the same manner as in Example 13, d
₃-3,5-Difluoro-4-chloro-1- [trans
-4- (trans-4-propylcyclohexyl) siku
2.0 g of lohexyl] benzene was obtained. Phase of this compound
The transition temperature and the D conversion rate are summarized in Table 1.

Example 15 d ₃ -4- (trans-
Synthesis of 2-butenyloxy) -1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene

[0097]

[Chemical formula 22]

D ₃ -4-methoxy-obtained in Example 9
2.0 g of 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was added to 2 g of acetic acid.
It was dissolved in 5 ml. Add 25 ml of 50% hydrobromic acid,
The mixture was heated and stirred under reflux for 24 hours. After cooling, the reaction solution was poured into ice water, the reaction product was extracted with toluene, and the extract solution was washed with a saturated sodium hydrogen carbonate aqueous solution and water. The solvent was distilled off, the resulting crude product was purified by recrystallization from hexane, d _{3-2,6-difluoro-4-} [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] 1.5 g of phenol was obtained. TH this
It was dissolved in F5 ml and added dropwise to 0.15 g of sodium hydride suspended in 20 ml of THF. After stirring for 30 minutes, 0.8 g of trans-2-butenyl bromide dissolved in 5 ml of THF was added dropwise, and the mixture was further heated with stirring under reflux of the solvent for 10 hours. After allowing to cool, water was added to decompose excess sodium hydride, and the reaction product was extracted with toluene. The extract was washed with dilute hydrochloric acid and water, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 1/10) to give d ₃ −4.
1.4 g of-(trans-2-butenyloxy) -1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained. The phase transition temperature and D conversion rate of this compound are summarized in Table 1.

Example 16 d ₃ -3,5-difluoro-4-methoxy-1- [trans-4- (trans-
4-propyl) cyclohexyl] Synthesis d ₄ 4- (trans-4-propyl-cyclohexyl benzene) cyclohexanone 4.4g and 4-bromo -
Analogously from 2,6-difluoro anisole 4.8g Example 9, d _{3-3,5-difluoro-4-methoxy-1-} [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene 6 0.0 g was obtained. The phase transition temperature and D conversion rate of this compound are summarized in Table 1.

Example 17 d ₃ -3,5-difluoro-4-difluoromethoxy-1- [trans-4-
Synthesis of (trans-4-propylcyclohexyl) cyclohexyl] benzene

[0101]

[Chemical formula 23]

3.0 g of d ₃ -3,5-difluoro-4-methoxy-1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] benzene obtained in Example 16 above was dissolved in 30 ml of dichloromethane. And cooled to 5 ° C. 1.5 g of anhydrous aluminum chloride was added and stirred for 3 hours. It was poured into ice water, extracted with toluene, and washed with a saturated aqueous sodium hydrogen carbonate solution and water.
The solvent was distilled off, the resulting crude product was recrystallized from hexane, d _{3-2,6-difluoro-4-} [trans -
2.6 g of 4- (trans-4-propylcyclohexyl) cyclohexyl] phenol was obtained. This was dissolved in 50 ml of toluene, 10 ml of formic acid and 0.2 g of p-toluenesulfonic acid were added, and the mixture was heated under reflux for 4 hours while removing distilled water. The reaction water, saturated aqueous sodium hydrogen carbonate solution, washed with water, the solvent was distilled off and recrystallized further from ethanol, d ₃ - formate 2,6-difluoro-4-
2.0 g of [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] phenyl was obtained. This was dissolved in 20 ml of dichloromethane and cooled to -15 ° C. 4 g of DAST was added to this, and it stirred for 2 hours.
It was poured into an aqueous solution of sodium hydrogen carbonate, the reaction product was extracted with dichloromethane, the extract was washed with water, dehydrated and dried, and then the solvent was distilled off under reduced pressure. The obtained crude product was subjected to silica gel column chromatography. (hexane / ethyl acetate = 1/20) as eluents, d _{3-3,5-difluoro-4-difluoromethoxy-1-} [trans-4
0.9 g of-(trans-4-propylcyclohexyl) cyclohexyl] benzene was obtained. The phase transition temperature and D conversion rate of this compound are summarized in Table 1.

Example 18 Preparation of Liquid Crystal Composition Base liquid crystal (A) having the following composition

[0104]

[Chemical formula 24]

(In the formula, the cyclohexane ring represents a trans configuration.) Shows a nematic (N) phase at 54.5 ° C. or lower. Obtained in Example 3 with 85% by weight of this host liquid crystal (A)

[0106]

[Chemical 25]

A mixed liquid crystal (B) containing 15% by weight of the compound of the above was prepared. The maximum temperature of the N phase of this composition is 6
It was 2.2 ° C. When this composition was stored at -20 ° C, precipitation of crystals could not be observed even after 1 month.

Comparative Example 2 The same host liquid crystal (A) 8 as described above
5% by weight and formula (R-1) not deuterated at all

[0109]

[Chemical formula 26]

A mixed liquid crystal (C) containing 15% by weight of the compound of the above was prepared. The maximum temperature of the N phase of this composition is 6
It was 2.3 ° C. Next, when this composition was stored at -20 ° C, precipitation of crystals was observed in 5 days.

Therefore, it is understood that the liquid crystal composition obtained by adding the mixture of the deuterium-substituted liquid crystal compounds of the present invention to the general-purpose host liquid crystal is unlikely to cause crystal precipitation even at low temperatures.

[0112]

EFFECTS OF THE INVENTION A mixture of deuterium-substituted cyclohexylcyclohexanone derivatives represented by the general formula (I) of the present invention, and a phenylbicyclohexane (CCP) derivative having the cyclohexane ring as an intermediate, deuterium-substituted The mixture can be easily produced industrially from commercially available compounds as shown in the examples.

Further, the liquid crystal composition containing the mixture of the compounds represented by the general formula (I) does not easily precipitate crystals even at a low temperature and has excellent compatibility with other liquid crystal compounds, so that it is practical. It is extremely useful as a constituent of liquid crystal materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C07C 43/21 7419-4H 43/215 7419-4H 43/225 C 7419-4H 255/50 9357- 4H 255/54 9357-4H

Claims (5)

[Claims] 1. A compound represented by the general formula (I):(In the formula, R¹Represents an alkyl group having 1 to 12 carbon atoms
Then Y¹And Y²Are each independently a hydrogen atom or
Represents an elementary atom, Z is a fluorine atom, a chlorine atom, cyano
Group, -R², -OR², -CF₃, -OCF₃, -OCF₂
H or -OCH₂CF ₃And R²Is 1 to 1 carbon atoms
12 alkyl groups or alkenyl having 2 to 12 carbon atoms
Represents a group, X¹, X²And X³Each independently, water
Represents an elementary atom (H) or a deuterium atom (D), but X¹,
X²And X³At least one of them is a deuterium atom (D)
The cyclohexane ring is in the trans configuration. )so
Two or more compounds selected from the group consisting of the represented compounds
The compound has (1) the number of deuterium atoms (D) and / or
Different substitution positions, and (2) R¹, Y¹, Y²Over
And Z are the same, the above general formula (I)
Two or more kinds selected from the group consisting of compounds represented by
A mixture of compounds. 2. In the general formula (I), R ¹ is a linear alkyl group having 1 to 7 carbon atoms, Z is a fluorine atom,
A chlorine atom, a cyano group, a linear alkyl group having 1 to 7 carbon atoms, an alkoxyl group, -OCF ₃ or -OCH ₂ CF ₃
The mixture according to claim 1, wherein 3. The total number of deuterium atoms (D) in two or more compounds selected from the group consisting of compounds represented by general formula (I) is based on the total number of X ¹ , X ² and X ³ . 5
The mixture according to claim 1, which is 0% or more. 4. A liquid crystal composition containing the mixture according to claim 1. 5. A compound represented by the general formula (II):(In the formula, R¹Represents an alkyl group having 1 to 12 carbon atoms
Then X¹, X², X³And X ^FourAre each independently hydrogen
Represents a child (H) or a deuterium atom (D), and X¹~ X^Fourof
At least one of them represents a deuterium atom (D),
The rohexane ring is in the trans configuration. )
Two or more compounds selected from the group consisting of compounds (1)
The number and / or substitution position of deuterium atoms (D) are different from each other.
And (2) R¹Are identical
A group consisting of the compound represented by the general formula (II)
A mixture consisting of two or more compounds selected from.